Chemical Engineering Journal 426 (2021) 131286

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Chemical Engineering Journal

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Cu-Zn oxides nanoparticles supported on SBA-15 zeolite as a novel

adsorbent for simultaneous removal of H2S and Hg0 in natural gas
Huawei Zhang a, *, Juan Wang b, Ting Liu a, *, Mingzhu Zhang b, Lifeng Hao c, *,
Thipphasone Phoutthavong b, Peng Liang b
a
School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033 PR China
b
College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590 PR China
c
Department of Engineering, Qiuzhen School, Huzhou University, Huzhou 313000, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Inspired by the fact that H2S can easily decompose on some metal oxides to form sulfur species and the resulting
Cu-Zn oxides products are usually used as Hg0 removal active sites, a novel Cu-Zn mixed oxide supported SBA-15 zeolite was
SBA-15 zeolite controllably synthesized for simultaneous removal of Hg0 and H2S. The Cu-Zn nanoparticles with a particle size
Simultaneous removal
range of 4.4–5.0 nm were successfully confined and uniformly dispersed in the two-dimensional mesopores of
Hydrogen sulfide
SBA-15. The obtained 1Cu1Zn/SBA-15 adsorbent presented an outstanding H2S and Hg0 removal efficiencies at
Elemental mercury
Natural gas 30 ◦ C and 30,000 h− 1, and the H2S and Hg0 capture capacities reached to 296.78 mg⋅g− 1 and 12.75 mg⋅g− 1 at a
10% breakthrough. In addition, the spent adsorbent could be regenerated in a 5% O2 and 95% N2 atmosphere at
600 ◦ C without obvious degradation of adsorption capacities over five cycles. We considered that the doping
effects of Cu-Zn oxides were beneficial for its excellent H2S and Hg0 removal performance at low temperatures,
and the nano-confinement effect of SBA-15 was conducive to prevent the oxides nanoparticles from agglomer­
ation in the regeneration process, thus achieving the outstanding regeneration performance. Furthermore, the
polysulfide polymer formed by chemisorption of H2S on the Cu-Zn oxides surface was confirmed to be the Hg0
active sites, which could react with gaseous mercury to form HgS. This work provided an effective way for
simultaneous removal of H2S and Hg0 in natural gas by confining nano-sized active metal oxides into the
mesopores of zeolites.

1. Introduction (MOFs) are considered to be effective for natural gas desulfurization.

As is known to us, hydrogen sulfide (H2S) and elemental mercury
(Hg0) are two typical toxic pollutants in natural gas, and their contents
usually vary from 4~1000 ppm and 1~200 µg⋅m− 3, which strongly
depended on the difference of production areas [1–3]. The presence of
H2S is generally considered as a significant question for chemical in­
dustry owing to its threat to human health, poisoning to the downstream
catalysts as well as corrosion to the equipment [4–7]. In addition, Hg0
also has caused a powerful threat to the environment because of its high
toxicity, strong volatility, biological enrichment and persistence for
decades [8,9]. Therefore, the concentrations of H2S and Hg0 in natural
gas should be limited lower than 2 ppm and 0.01 µg⋅m− 3 to meet the
requirements of subsequent utilization processes.
Currently, a series of adsorbents such as activated carbon (AC),
molecular sieves, metal oxides and metal organic framework materials
Hernández et al. [10] investigated that the activated carbon supporting
10 wt% of ZnO was better than the industrial activated carbon for
desulfurization capability in the presence of an air stream containing
200 ppm of H2S at ambient temperature. The Zn/MSU-1 and Cu/MSU-1
adsorbents were prepared with the incipient wetness method by Montes
et al. [11] to remove H2S, and they found that the addition of Zn and Cu
improved the removal capacity of H2S of MSU-1, which reached to the
adsorption capacity of 42.3 mg∙g− 1 (10Zn/MSU-1) and 19.2 mg∙g− 1
(20Cu/MSU-1), respectively. Liu et al. [12] constructed a Zn/SiO2
composite material with a loading of different active components, which
exhibited an excellent H2S removal performance with a sulfur capacity
of 94.4 mg∙g− 1. Bhatt et al. [13] demonstrated that the rare earth metal
oxides-based MOFs showed an excellent removal performance for H2S.
At the same time, some sulfur modified activated carbon [14,15] and
metal sulfides [16–18] are usually selected as demercuration agents.

* Corresponding authors.
E-mail addresses: sdkdzhw@163.com (H. Zhang), 07liuting@163.com (T. Liu), 02578@zjhu.edu.cn (L. Hao).

https://doi.org/10.1016/j.cej.2021.131286
Received 6 May 2021; Received in revised form 5 July 2021; Accepted 8 July 2021
Available online 12 July 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
H. Zhang et al.
Among them, metal sulfides are widely used due to their abundant sulfur
active sites, environmental friendliness and low cost. Zhao et al. [19]
prepared the CoMoS/γ-Al2O3 adsorbent through initial wetting and
sulfurization treatment methods, and achieved an almost 100% of Hg0
removal efficiency at 50 ◦ C. Meanwhile, its capture capacity reached to
18.95 mg∙g− 1, and the MoS2 nanosheets with two-dimensional structure
were proved to be the mercury active sites, in which sulfur atoms were
tend to combine with Hg0 to form HgS. Li et al. [20] prepared ZnS nano-
particles with a specific surface area of 196.1 m2∙g− 1 and its capture
capacity of Hg0 achieved 497.84 µg∙g− 1, which was benefited by the
affluent sulfur sites of ZnS and the high binding affinity for Hg0. Liu et al.
[21] developed many adsorbents for Hg0 removal experiments, the re­
sults indicated that the Hg0 capture capacity of different adsorbents was
CuS ˃ MnS ˃ SnS ˃ ZnS ˃ CdS. In particular, the adsorption capacity of
CuS reached to 50.17 mg∙g− 1 at 50 ◦ C at a 50% breakthrough.
Up to now, some researches have revealed that the Hg0 removal
performance can be significantly improved when the raw gas contained
a certain amount of H2S [22]. For instance, Chen et al. [23] elaborated
that the existence of H2S could drastically improve the Hg0 removal
capacity of porous carbon, which was due to the formation of stable HgS.
The H2S was introduced into the CeO2/TiO2 adsorbent prepared by Zhou
et al. [24], and its Hg0 removal efficiency reached to 98% by the for­
mation of active sulfur species and further reaction with gaseous mer­
cury on the adsorbent. The nano-sized ZnO has a wide application
prospect due to its advantages of quantum size effect, good thermody­
namic properties (ΔG298K = 76 kJ/mol) and high equilibrium constant,
and it also has the characteristics of high accuracy, stability and reli­
ability as a desulfurizing agent [25–27]. In addition, the doping of other
metal oxides on ZnO is generally considered to be favorable for the
improvement of desulfurization performance due to the increase of
active sites and promotion of dispersion. Yang et al. [26] constructed a
stable and sustainable adsorbent by doping Co species into ZnO/SiO2 a
sulfur capture capacity of 118.4 mg∙g− 1. Jiang et al. [28] prepared Zn-
Cu mixed metal oxides and the highest sulfur adsorption capacity
reached to 257 mg∙g− 1 at 40 ◦ C. Therefore, it is a promising way to
remove H2S and Hg0 simultaneously using metal oxides loaded adsor­
bents in nature gas. Because of the advantages of large surface area,
narrow pore size distribution and adjustable pore structure, molecular
sieve has become a hot spot of adsorbent carrier in many fields. The
skeleton type, defect location and surface properties in molecular sieve
(SBA-15) were used to load metal oxides for preparing highly efficient
adsorbents, and the adsorbents had excellent regeneration performance
owning to the confinement effect of the pores of molecular sieves.
In this work, a series of xCuyZn/SBA-15 adsorbents were controlled
and synthetized by a simple sol–gel method to explore the simultaneous
removal of H2S and Hg0 in natural gas at room temperature. By con­
trasting the chemical and physical properties of the prepared adsor­
bents, this paper offers an intensive understanding of the H2S and Hg0
removal performance on the adsorbent and provides adsorbent regen­
eration for the application of xCuyZn/SBA-15 adsorbents. Combining
with the conditions of space velocities and reaction temperature in
capturing H2S and Hg0, a series of experiments are performed to
investigate the probable tolerance of different conditions, offering a
sufficient explanation on the practical application in natural gas.
Furthermore, Hg-TPD result and XPS analysis were analyzed to study the
probable intermediate products to propose the underlying mechanism of
simultaneous removal of H2S and Hg0 on the xCuyZn/SBA-15 adsorbent.
2. Materials and methods
2.1. Preparation methods of the adsorbents
The xCuyZn/SBA-15 adsorbents with total metal oxides loading
content of 30 wt% and molar ratios x:y of 1:4, 1:2, 1:1 and 2:1 were
prepared by sol–gel methods and named as 1Cu4Zn/SBA-15, 1Cu2Zn/
SBA-15, 1Cu1Zn/SBA-15 and 2Cu1Zn/SBA-15, respectively. Taking the
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Chemical Engineering Journal 426 (2021) 131286
preparation of 1Cu1Zn/SBA-15 adsorbent as an example. Firstly, 0.803 g
of Zn(NO3)2⋅6H2O and 0.652 g of Cu(NO3)2⋅3H2O were sufficiently
dissolved in 25 mL of nitric acid solution (0.2 mol/L) to avoid hydro­
lysis. After adding citric acid with 1.5 times molar amount of total metal
ions as complexing agent, 1.000 g of SBA-15 zeolite was mixed into the
solution and continuously stirred until the existence of sol. Secondly, the
mixed sol was remained in a water bath at 60 ◦ C for incessant evapo­
ration and stirring to obtain blue gel, which was aged for 72 h at 30 ◦ C.
Finally, the obtained product was dried for 12 h at 100 ◦ C and calcined
for 4 h at 450 ◦ C in a muffle furnace, and then the resulted sample was
expressed as 1Cu1Zn/SBA-15. The 1Cu4Zn/SBA-15, 1Cu2Zn/SBA-15
and 2Cu1Zn/SBA-15 adsorbents involved in the work were obtained
according to the same preparation process. The spent adsorbent after
simultaneous removal of H2S and Hg0 was named as S-xCuyZn/SBA-15.
In the pre-treatment, the 1Cu1Zn/SBA-15 adsorbent was pretreated with
200 ppm of H2S for 4 h, then named as H2S-1Cu1Zn/SBA-15, which
would be recorded as Hg0-H2S-1Cu1Zn/SBA-15 after Hg0 removal test
for 10 h.
2.2. Characterization of synthesized adsorbents
The physico-chemical properties of adsorbents were characterized
using a series of different characterization methods such as Inductively
coupled plasma (ICP), N2 adsorption–desorption isotherms (BET), X-ray
diffraction (XRD), High-resolution transmission electron microscopy
(HRTEM), Scanning electron microscopy (SEM) and X-ray photoelectron
spectroscopy (XPS). The operation details of each characterization
technique are provided in the Supplementary Material.
2.3. Evaluation tests of adsorbents for H2S and Hg0 removal
The experimental device for simultaneous removal of H2S and Hg0
was appeared in Fig. 1. All the evaluation experiments of the prepared
adsorbents were developed in the fixed bed reactor with a temperature
control device, in which the target adsorbent with a mass of 0.2 g was
put and a whole gas flow of 1.0 L⋅min− 1 containing about 100 μg⋅m− 3 of
mercury vapor produced by the mercury penetrant unit and 200 ppm of
H2S was introduced. The CH4 content occupies 98% and remaining gas
in gas flow is N2, meanwhile, the influence of CH4 as well as the blank
tests with and without H2S were also carried on in exploring the accurate
mechanism and capture effect. The mercury analyzer (RA-915, Lumex,
Inc. Russia) and gas chromatography (Shimadzu, GC2010) were applied
to monitor the concentration of Hg0 and H2S before and after adsorption
reactions, respectively. The exhaust gas was discharged into the atmo­
sphere after being treated with activated carbon. After adsorption
experiment, the spent adsorbent was regenerated by heat treatment in
95% N2 and 5% O2 atmosphere and its H2S and Hg0 capture efficiencies
were investigated to measure the regeneration performance.
Before the adsorption experiment, the stable concentrations of H2S
and Hg0 were continuously introduced into the system to establish the
basic mass balance and ensure the authenticity and reliability of test
data. Moreover, each of experiment was duplicated three times with the
standard deviation of 0.81% to guarantee the accuracy of the data. The
efficiencies of the prepared adsorbent for the removal of H2S and Hg0
can be defined by Eq. (1).
Cin − Cout
η= × 100% (1)
Cin
η: the removal efficiencies of H2S and Hg0; Cin: the inlet concentrations
of H2S (ppm) and Hg0 (µg⋅m− 3), Cout: the outlet concentrations of H2S
(ppm) and Hg0 (µg⋅m− 3).
Furthermore, the stability evaluation experiments for H2S and Hg0
removal were performed at 30 ◦ C and 30,000 h− 1 to calculate the H2S
and Hg0 capture capacities of the adsorbents. In this work, the capture
capacities were determined as the mass of adsorbed H2S or Hg0 by the
H. Zhang et al. Chemical Engineering Journal 426 (2021) 131286

Fig. 1. Experimental setup for simultaneous removal of H2S and Hg0.

per unit mass of adsorbent when the removal efficiencies of both H2S shift to higher angle, which is mainly due to the higher condensation
and Hg0 reached 90% (expressed as 10% breakthrough). The Eq. (2) and degree of silicate caused by the interaction between metal oxides and
Eq. (3) are as follows: silica substrates. As shown in Fig. 2b, the new peaks at 35.6◦ , 38.8◦ ,
∫t 48.7◦ , 53◦ , 58.3◦ , 61.6◦ , 66.1◦ and 68.1◦ appear in the spectrum of
Cin Lt − 0 Cout Ldt 1Cu1Zn/SBA-15 sample, which are associated with the ( − 1 1 1), (1 1 1),
q= × 10− 6 (2)
m ( − 2 0 2), (0 2 0), (2 0 2), ( − 1 1 3), (0 2 2) and (2 2 0) crystal planes of
( ∫t ) monoclinic crystal structure CuO [30]. Moreover, there is only a weak
LM s × Cin t − 0 Cout dt
Q= (3) diffraction peak of ZnO (1 0 0) crystal plane, indicating the small size and
1000mVL
uniform dispersion of the doped ZnO nanoparticles. Furthermore, metal
oxides with a total mass of 30 wt% were loaded by sol–gel method
Q: the capture capacity of H2S (mg⋅g-1); q: the capture capacity of Hg0
during the preparation of the 1Cu1Zn/SBA-15 adsorbent, and ICP
(mg⋅g-1); Cin: the inlet concentrations of H2S (ppm) and Hg0 (µg⋅m-3);
analysis detected 14.03 wt% and 14.64 wt% of Cu and Zn in the
Cout: the outlet concentrations of H2S (ppm) and Hg0 (µg⋅m-3) in the fixed
1Cu1Zn/SBA-15 adsorbent, indicating that the Cu and Zn nanoparticles
bed reactor; Ms: the molar mass of H2S (34 g⋅mol-1); VL: the molar vol­
are successfully loaded on the SBA-15 zeolite. Compared to the 1Cu1Zn/
ume of gas (24.45 L⋅mol-1); t: the adsorption time (min); m: the mass of
SBA-15 adsorbent, it is obviously that the diffraction peak intensity of
adsorbent (g), L: the gas flow rate (L⋅min-1).
CuO and ZnO in the XRD spectrum of S-1Cu1Zn/SBA-15 decreases
dramatically, which implies that the lattice structure of CuO and ZnO
3. Results and discussion
are destroyed in the process of the adsorption reaction for H2S and Hg0.
Besides, the diffraction peaks at 25.8◦ , 27.8◦ , 32.7◦ , 35.9◦ and 44.2◦ in
3.1. Characterization of the adsorbents
Fig. 2c demonstrate the existence of sulfur species on the spent adsor­
bent. The characteristic peaks of mercury are not observed in the XRD
The low-angle and wide-angle X-ray diffraction spectra of the SBA-
pattern of S-1Cu1Zn/SBA-15 sample, which is due to the lower mercury
15, 1Cu1Zn/SBA-15 and S-1Cu1Zn/SBA-15 samples are presented in
content.
Fig. 2. The three characteristic diffraction peaks of 0.9◦ , 1.7◦ and 2.0◦ in
The porosity structure of the adsorbents is tested by nitrogen
Fig. 2a are consistent with the (1 0 0), (1 1 0) and (2 0 0) crystal planes of
adsorption–desorption isotherm and pictured in Fig. 3. All the samples
SBA-15 [29]. It can be seen that the hexagonal arrangement of SBA-15
have reversible type IV isotherms based on the IUPAC classification [31]
skeleton retains intact after the loading of Cu-Zn oxides while the
with a typical H1-type hysteresis loop and an evident bending at P/P0 =
diffraction peak is broadened with a slight decrease in intensity and a

Fig. 2. XRD patterns of samples, a: SBA-15; b: 1Cu1Zn/SBA-15 and c: S-1Cu1Zn/SBA-15.

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H. Zhang et al.
Fig. 3. The porosity structure of SBA-15, 1Zn1Cu/SBA-15 and S-1Zn1Cu/SBA-15 samples: (a) N2 adsorption–desorption isotherms; (b) pore size distributions.
0.70 in the Fig. 3a, which is the characteristic of capillary condensation
in uniform mesopores [32]. Compared to the SBA-15, the hysteresis loop
height of 1Cu1Zn/SBA-15 and S-1Cu1Zn/SBA-15 adsorbents decrease
obviously, which mainly due to the blockage of partial of mesopores
caused by metal oxides modification as well as H2S and Hg0 adsorption
process. The pore size distribution of SBA-15 in Fig. 3b ranges from 6 to
8 nm and decreases to 3–7 nm after the loading of Cu-Zn mixed oxides.
This is because that the adsorption of H2S and Hg0 have a negligible
effect on the pore distribution of 1Cu1Zn/SBA-15 adsorbent. The BET
parameters of all samples are shown in Table 1. The specific surface
area, pore volume and average pore diameter of SBA-15 are 700 m2/g,
0.971 cm3/g and 6.51 nm, respectively. Compared with SBA-15, the
specific surface area and total pore volume of 1Cu1Zn/SBA-15 are
significantly reduced by 57% and 47.9% because of partial blockage of
the SBA-15 sieve pore channels. The evident reduction of micropores
volume proves that the micropores are preferentially filled, causing the
increased average pore diameter with the addition of active substance.
The decrease of mesopore volume and the increase of micropore volume
demonstrates that the adsorption reaction happens in mesoporous, and
the average pore diameter is decreased owning to the mesopore
blockage.
The SEM image in Fig. 4a shows the ordered small rod-like sub-
particles of SBA-15 sample, which is similar with the study of Katiyar
et al. [33]. The HRTEM images of SBA-15 in Fig. 4b shows that the
distance between the two dark strips of SBA-15 sample is about 7 nm,
which is consistent with the pore size distribution in N2 adsorp­
tion–desorption results. Fig. S1 reveals an ordered hexagonal meso­
porous array when the electron beam is parallel to the cylindrical pores.
The clear channels can be observed from Fig. 4c that when the electron
beam is perpendicular to the cylindrical pores, it owns a highly ordered
two-dimensional pore structure. It is illustrated that the nanoparticles of
ZnO and CuO uniformly disperse inner the channels of 1Cu1Zn/SBA-15
mesopoers with no obvious aggregation in Fig. 4d. Furthermore, the
(1 0 0) plane of ZnO with a lattice spacing of 0.282 nm as well as the
(− 1 1 1) and (1 1 1) planes of CuO with a lattice spacing of 0.252 nm and
0.232 nm could be determined from Fig. 4f [34]. The particle size dis­
tribution in Fig. 4e demonstrates the particle size of 4.4–5.0 nm in
supported Cu-Zn oxides.
The XPS spectra of 1Cu1Zn/SBA-15 sample is shown in Fig. 5. As our
Table 1
The calculated contents of adsorbed sulfur species on samples.
S2- S2-
n S8 SO2-
4
H2S-1Cu1Zn/SBA-15 31.47% 40.29% 17.55% 10.69%
Hg0-H2S-1Cu1Zn/SBA-15 38.29% 28.32% 18.96% 14.43%
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Chemical Engineering Journal 426 (2021) 131286
anticipation, the peaks of Si2p, O1s, C1s, Zn2p and Cu2p appears in the
full XPS spectrum of 1Cu1Zn/SBA-15 (Fig. 5a), indicating the successful
load of Cu-Zn mixed oxides on SBA-15 zeolite. Fig. 5b presents the
narrow Zn2p spectrum of 1Cu1Zn/SBA-15, and the two peaks located at
1045.3 eV and 1022.3 eV are attributed to the characteristic peaks of
Zn2p1/2 and Zn2p3/2, respectively. For the XPS spectrum of Cu2p, the
peaks locate at 953.6 eV and 933.5 eV, which is corresponded to Cu2p1/
2 and Cu2p3/2 in Fig. 5c, and the peaks at 962.3 eV and 942.3 eV are
assigned to the satellite [35]. The O1s narrow spectrum in Fig. 5d could
be fitted by the peaks of 532.4 eV and 533.2 eV, attributing to the lattice
oxygen (Oβ) and chemisorbed oxygen (Oα) [36]. It is calculated that the
contents of Oβ and Oα are 72.8% and 27.2%, respectively.
3.2. The simultaneous removal performance of H2S and Hg0 over
xCuyZn/SBA-15 adsorbents
Fig. 6 gives the simultaneous removal performance of Hg0 and H2S
over adsorbents with different Cu/Zn mole ratios (1:4, 1:2, 1:1 and 2:1)
at 30,000 h− 1 and at 30 ◦ C. It can be observed form Fig. 6a that the four
adsorbents exhibit a perfect Hg0 removal efficiency at the beginning of 4
h. When the reaction time is lengthened to 10 h, the Hg0 removal effi­
ciencies of 1Cu4Zn/SBA-15, 1Cu2Zn/SBA-15 and 2Cu1Zn/SBA-15 ad­
sorbents is 98.97%, 98.80% and 99.05%, respectively, however, the
1Cu1Zn/SBA-15 sample still remains an excellent Hg0 capture perfor­
mance of 100%. It can be seen from Fig. 6b that the Cu/Zn mole ratio has
a crucial impact on H2S removal performance, and the H2S removal
efficiencies of four adsorbents decrease gradually with the increase of
adsorption time. In this work, the saturated adsorption time is used to
determine the H2S removal performance, which is confirmed as the H2S
breakthrough threshold arrived at 10%. It is evidently that the saturated
adsorption time of four adsorbents with different Cu/Zn mole ratios
(1:4, 1:2, 1:1 and 2:1) is 150, 200, 240 and 210 min, respectively. Thus,
we draw the conclusion that the 1Cu1Zn/SBA-15 adsorbent has the best
simultaneous removal performance of Hg0 and H2S.
3.3. The H2S and Hg0 removal performance of 1Cu1Zn/SBA-15
adsorbent
Fig. 7 presents the simultaneous removal efficiencies and capacities
of H2S and Hg0 of SBA-15 and 1Cu1Zn/SBA-15 adsorbents. As illustrated
in Fig. 7a, the Hg0 removal efficiency of the SBA-15 decreases from
100% to 10% after 6 h, and the H2S removal efficiency drops rapidly to
5% after 120 min, suggesting its poor H2S and Hg0 capture performance,
which is probably caused by the absence of adsorption active sites.
However, the Hg0 removal efficiency of 1Cu1Zn/SBA-15 adsorbent
almost remains at 100% after 10 h, and the H2S removal efficiency drops
H. Zhang et al. Chemical Engineering Journal 426 (2021) 131286

Fig. 4. a-c: SEM images and HRTEM images of SBA-15; d-f: HRTEM images of 1Cu1Zn/SBA-15 absorbent; e: Particle size distribution of Cu and Zn in1Cu1Zn/SBA-
15 absorbent.

Fig. 5. XPS spectra of the 1Cu1Zn/SBA-15: (a) Full XPS spectrum, (b) Zn2p, (c) Cu2p, (d) O1s.

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H. Zhang et al.
Fig. 6. The Hg0 (a) and H2S (b) removal performance of asorbents with different ratios of Cu and Zn.
Fig. 7. The H2S and Hg0 removal performances of SBA-15 and 1Cu1Zn/SBA-15 absorbents: a: H2S and Hg0 removal efficiencies; b: H2S and Hg0 adsorption capacities
at 10% breakthrough; c: The Hg0 removal efficiency with and without H2S.
slowly to 90% after 240 min, which is superior to the SBA-15 sample.
The great superiority is mainly due to the loaded Cu-Zn mixed oxides
could firstly react as active sites for desulfurization, and the resultant
sulfur and sulfide species have a strong adsorption property for Hg0
[37,38].
The H2S and Hg0 capture capacity are defined as the H2S and Hg0
mass adsorbed by per unit mass of adsorbent at the adsorption effi­
ciencies of 90%, and the calculated results of H2S and Hg0 capture ca­
pacities are exhibited in Fig. 7b. The H2S and Hg0 adsorption capacity of
SBA-15 sample are only 7.3 mg⋅g− 1 and 24 µg⋅g− 1. However, the
1Cu1Zn/SBA-15 adsorbent presents a H2S capture capacity of 296.78
mg⋅g− 1 and a Hg0 capture capacity of 12.75 mg⋅g− 1, respectively, much
higher than SBA-15 as well as Hg0 adsorbents (MnOx/graphene, 2.7
mg⋅g− 1) [39] and H2S adsorbents (Zn/SiO2, 96.4 mg⋅g− 1) [12]. In
addition, it is observed that the H2S plays a key role in Fig. 7c on the
1Cu1Zn/SBA-15 adsorbent, in which the Hg0 removal efficiency is
obviously captured in the presence of H2S.
We consider that the excellent H2S and Hg0 removal performance as
well as large capture capacity of 1Cu1Zn/SBA-15 are benefited from the
synergistic effect of Cu-Zn mixed oxides and the appropriate doping
amounts of Cu and Zn, which is also confirmed by other researchers. For
instance, Yang et al. [40] compared the H2S capacity of ZnO/SiO2 mixed
different metallics at room temperature and concluded that the Cu
doping in adsorbent showed the largest H2S capacity. Baird et al. [41]
indicated that Cu and Co dopants improved the H2S removal ability of
ZnO at 30 ◦ C. Therefore, the doping of Cu-Zn in mixed oxides is a
promising way for controllable synthesis of adsorbents in simulta­
neously removing Hg0 and H2S at low temperatures in natural gas.
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Chemical Engineering Journal 426 (2021) 131286
3.4. Regeneration performance of 1Cu1Zn/SBA-15 adsorbent
The spent 1Cu1Zn/SBA-15 adsorbent was regenerated in the tube
furnace through heat treatment at 600 ◦ C for 1 h, meanwhile, the mixed
atmosphere of 5% O2 and 95% N2 was selected to effectively prevent the
formation of sulfate. The low oxygen content in regenerated atmosphere
effectively prevents the formation of sulfate, which is beneficial for the
regeneration performance of S-1Cu1Zn/SBA-15 sample. Then, 5
continuous adsorption-regeneration cycles were carried out to study the
regeneration performance of 1Cu1Zn/SBA-15. Finally, the H2S and Hg0
removal efficiencies of the regenerated adsorbents were calculated after
1 h of adsorption reaction.
As pictured in Fig. 8a that the Hg0 removal efficiency yet keeps stable
at 100% while the Hg0 capture capacity decreases from 12.75 mg⋅g− 1 to
12.08 mg⋅g− 1 after 5 regeneration cycles. Fig. 8b exhibits that the re­
generated adsorbents also perform a complete H2S removal efficiency,
however, its H2S capture decreases to 254.8 mg⋅g− 1 after 5 regeneration
cycles, which is 85.96% of the initial H2S capture capacity in fresh
adsorbent. The loss of H2S capture capacity after regeneration is mainly
due to the fact that the regeneration temperature (600 ◦ C) is higher than
the calcination temperature (450 ◦ C) in adsorbent preparation process,
resulting in partial sintering and slight aggregation of the active
component.
3.5. Effect of space velocities on H2S and Hg0 removal performance of
adsorbents
The high space velocities tolerance tests of SBA-15 and 1Cu1Zn/SBA-
15 were investigated at 30 ◦ C, the H2S and Hg0 removal efficiencies were
H. Zhang et al. Chemical Engineering Journal 426 (2021) 131286

Fig. 8. Regeneration results of the 1Cu1Zn/SBA-15 absorbent.

calculated after 1 h of adsorption time at each space velocity. The H2S

and Hg0 removal efficiency of SBA-15 sample decreases gradually with
the increase of space velocities in Fig. 9. When the space velocity in­
creases from 10,000 h− 1 to 60,000 h− 1, the H2S and Hg0 removal effi­
ciencies of the SBA-15 decrease from 68.3% and 88.0% to 28.2% and
38.4%, respectively. However, the 1Cu1Zn/SBA-15 adsorbent shows an
excellent tolerance to high space velocities, and the removal efficiencies
of H2S and Hg0 are nearly stable at 100% in 10,000~40,000 h− 1. As the
space velocity increases to 60,000 h− 1, its H2S and Hg0 removal effi­
ciencies decrease slightly to 95.1% and 99.0%, respectively. The toler­
ance to high space velocities in 1Cu1Zn/SBA-15 adsorbent is mainly
attributed to its developed pore structure and highly dispersed metal
oxides.

3.6. Effect of temperatures on H2S and Hg0 removal efficiencies of

adsorbents

The H2S and Hg0 removal efficiencies of 1Cu1Zn/SBA-15 at different

adsorption temperatures were measured at 30–150 ◦ C and defined as the
total content in one hours. It can be seen that the increase of adsorption
temperature has little influence on H2S removal efficiency in Fig. 10,
which remains stable. In terms of the Hg0 removal, the 1Cu1Zn/SBA-15
adsorbent presents a complete removal from 30 ◦ C to 90 ◦ C, then de­
creases gradually as the adsorption temperature increased further and
reaches to 92.0% at 150 ◦ C. Although the increase of temperature has a
negative influence on Hg0 removal efficiency of 1Cu1Zn/SBA-15, its Hg0
Fig. 10. Influence of temperature on Hg0 and H2S removal efficiencies of
1Cu1Zn/SBA-15.
removal performance at high temperature is still superior to some
existing metal oxides supported adsorbents such as Fe2O3/TiO2 (70% at
150 ◦ C) [42] and coal-based AC (80% at 150 ◦ C) [43]. Generally
speaking, the 1Cu1Zn/SBA-15 adsorbent has a relative wide tempera­
ture window for H2S and Hg0 removal, which allows its potential for
desulfurization and demercuration in syngas at higher temperatures.

3.7. Mechanism of H2S and Hg0 removal over 1Cu1Zn/SBA-15

adsorbent

Fig. 9. Influence of space velocity on H2S and Hg0 removal performance
of absorbents.
The Hg-TPD experiment and XPS analysis were adopted on the spent
adsorbent to explore the H2S and Hg0 simultaneous removal mechanism.
The full XPS spectrum of S-1Cu1Zn/SBA-15 sample in Fig. 11a shows a
weak S2p peak at 161.9 eV, which is caused by the transition of H2S to
surface adsorbed sulfur species and could be as an evidence for H2S
adsorption on the 1Cu1Zn/SBA-15 adsorbent. As depicted in Fig. 11b,
the narrow Zn2p spectrum of S-1Cu1Zn/SBA-15 includes two peaks of
Zn2p3/2 at 1021.8 eV and Zn2p1/2 at 1045.2 eV and shifts to lower
binding energy by 1022.3 eV and 1045.3 eV compared with those of in
1Cu1Zn/SBA-15, respectively. The result after Hg0 and H2S adsorption
reveals the change in chemical environment of Zn2+, which can be
interpreted as a conversion from ZnO to –S–S–Zn [44]. At the same time,
the Cu2p3/2 at 931.9 eV and Cu2p1/2 at 951.8 eV in Fig. 11c also de­
creases slightly to lower binding energy after the adsorption reaction,

7
H. Zhang et al. Chemical Engineering Journal 426 (2021) 131286

Fig. 11. a: Full spectrum of S-1Cu1Zn/SBA-15 sorbent; b-e: XPS spectra of Zn2p, Cu2p, S2p and O1s for S-1Cu1Zn/SBA-15 sorbent; f: The Hg-TPD curves of S-
1Cu1Zn/SBA-15 sorbent.

indicating that Cu2+ is partially reduced to Cu+ in the adsorption process
[21].
In previous study [45], we have revealed that the Hg0 and H2S
capture on metal oxides follows the Eley-Rideal mechanism by density
functional theory calculations and experimental research, where the H2S
was chemically adsorbed on the metal oxides to produce active sulfur
species, and then reacted with the adsorbed Hg0 to form HgS. However,
what kind of adsorbed sulfur species are easily reacted with Hg0, and
what is the underlying specific reaction mechanism are still unclear up
to now. Han et al. [46] believed that the elemental sulfur was produced
by gaseous H2S and Fe2O3, leading to an increase of mercury removal
efficiency. Based on XPS analysis, Liu et al. [47] deduced that Cu2+ and
S2- of CuS microsphere were the critical factor for Hg0 capture. The XPS
spectrum of H2S-1Cu1Zn/SBA-15 (Fig. 11d) composes of four peaks
centered at 161.68 eV, 162.72 eV, 163.8 eV and 168.2 eV, which are
ascribed to sulfur species of S2− , elemental sulfur (S8), polysulfide
polymer (S2− 2− 0
n ) and SO4 , respectively [48]. After Hg adsorption, it is
0
evidently from XPS spectrum of Hg -H2S-1Cu1Zn/SBA-15 sample and
Table 2 that the S2- n content decreases dramatically from 40.29% to
28.32%, while the S2- and SO2− 4 contents increases slightly from 31.47%
and 10.69% to 38.92% and 14.43%, respectively. It is speculated that
the S2− 0
n are the active sites as well as key contributor for Hg capture and
0 2−
can easily react with gaseous Hg to generate HgS, meanwhile, some
sulfates are also formed [49].
In addition, the O1s spectrum of spent adsorbent is fitted by three
peaks of 533.2 eV, 532.4 eV and 533.9 eV, assigning to the chemisorbed
Table 2
The contents of oxygen species on 1Cu1Zn/SBA-15 and S-1Cu1Zn/SBA-15
samples.
Oβ (lattice Oα (chemisorbed Oγ (adsorbed
oxygen) oxygen) H2O)
oxygen (Oα), lattice oxygen (Oβ) and the oxygen of adsorbed H2O (Oγ),
respectively. In Table 2, it is clear that the contents of Oα and Oβ in fresh
adsorbent decreased from 27.2% and 72.8% to 21.0% and 66.3% after
reaction, indicating that partial of Oα and Oβ are consumed in the
simultaneous removal of H2S and Hg0. Furthermore, the presence of
21.7% Oγ suggests the reaction of Oα and Oβ between metal oxides with
H2S and the formation of H2O during the adsorption process[24].
In order to research the mercury species on the spent adsorbent, the
fresh 1Cu1Zn/SBA-15 was used for 1 h of adsorption in the condition of
100 μg⋅m− 3 of Hg0 and 200 ppm of H2S. The obtained sample was
characterized by Hg-TPD method with a heating rate of 5 ◦ C/min and an
atmosphere of pure N2 at 30–400 ◦ C. The Hg0 release temperature of the
spent adsorbent ranges from 220 ◦ C to 350 ◦ C with a release peak center
of 290 ◦ C in Fig. 11f, and the Hg release curve could be divided into the
peaks of 269 ◦ C and 310 ◦ C, corresponding to the decomposition of black
HgS and red HgS [50,51], respectively. The Hg-TPD results demonstrate
that the formation of adsorbed Hg0 is mainly stable HgS on the surface of
spent 1Cu1Zn/SBA-15 adsorbent.
As mentioned above, the mechanism of simultaneous removal of H2S
and Hg0 over the 1Cu1Zn/SBA-15 adsorbent is shown in Fig. 12 and Eq.
(4–7). The gaseous H2S is firstly adsorbed and dissociated on the Cu-Zn
oxides surface to generate sulfur species of S2− , S8, S2− 2−
n and SO4 , and
0
then the Sn reacts with adsorbed Hg to form stable HgS.
(4)
Cuzn/SBA− 15
H2 S(g) ̅̅̅̅̅̅̅̅̅̅→ HS(g) + H(g)
(5)
Cuzn/SBA− 15
HS(g) ̅̅̅̅̅̅̅̅̅̅→ S(s, g) + H(g)
Cuzn/SBA− 15
Hg0 (g) → Hg0 (s, g) (6)
Cuzn/SBA− 15
Hg0 (s, g) + S(s, g) → HgS(s) (7)

contents of 72.8% 27.2% 0.0% 4. Conclusions

fresh
contents of 66.3% 21.0% 12.7%
Considering the significant synergistic effect of H2S and Hg0 removal
spent

8
H. Zhang et al.
Fig. 12. Mechanism of simultaneous removal H2S and Hg0 over the 1Cu1Zn/SBA-15 absorbent.
on the surface of metal oxides, the xCuyZn/SBA-15 adsorbents, which
combined with the advantages of high desulfurization accuracy, large
sulfur capacity and good regeneration performance, were prepared
using sol–gel method to effectively and economically capture H2S and
Hg0 in natural gas. It was found that the prepared 1Cu1Zn/SBA-15
adsorbent exhibited the best removal performance of H2S and Hg0,
large capture capacity, wide operating temperature window and excel­
lent regeneration property. Under the operation conditions of 30 ◦ C and
30,000 h− 1, the 1Cu1Zn/SBA-15 adsorbent presented a complete
removal of H2S and Hg0 and the corresponding adsorption capacities
arrived at 296.78 mg⋅g− 1 and 12.75 mg⋅g− 1 at a 10% breakthrough,
which were well above than most of the commercial adsorbents.
It is equally important that the spent adsorbent can be easily re­
generated by thermal treatment in a 5% O2 and 95% N2 atmosphere at
600 ◦ C for 1 h. After 5 regeneration cycles, the H2S and Hg0 capture
capacities decreased slightly by 14.04% and 5.24%, respectively.
Furthermore, the Hg-TPD and XPS results implied that the H2S could be
chemisorbed on the surface of Cu-Zn mixed oxides and formed sulfur
species such as S2− , elemental sulfur (S8), polysulfide polymer (S2−
n ) and
SO2− 2−
4 . Among them, the Sn compounds were proved to be the main
active sites and key contributor for gas Hg0 capture. Thus, the 1Cu1Zn/
SBA-15 adsorbent is supposed to be a perspective composite material for
simultaneous removal of H2S and Hg0 in natural gas at low temperature.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (22078168, 21776164), the Qingchuang Science and Tech­
nology Program of Shandong Province University (2019KJD004), the
Natural Science Foundation of Shandong Province (ZR2019MEE023)
and the Natural Science Foundation of Huzhou (2020GZ04, 2019KT26).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.131286.
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